Meta-anilide urea compositions and their utility as herbicides

ABSTRACT

META-ANILIDE UREA COMPOSITIONS HAVE THE FORMULA:   1-(R2-N(-R3)-C(=X)-N(-R1)-),3-(R5-C(=Y)-N(-R4)-),(Z)M-   BENZENE   IN WHICH X AND Y ARE, INDEPENDENTLY, OXYGEN AND SULFUR; R1 IS HYDROGEN OR LOWER ALKYL; R2 AND R3 ARE, INDEPENDENTLY, HYDROGEN, ALKYL, LOWER ALKOXY, HALOALKYL, LOWER ALKENYL, CYCLOALKYL HAVING FROM 3 TO 6 CARBON ATOMS, INCLUSIVE, CARBALKOXYALKYL, FURFURYL, NAPHTHYL, PHENYL OR SUBSTITUTED-PHENYL, INCLUSIVE, IN WHICH THE SUBSTITUENTS ARE HALOGEN, NITRO, OR LOWER ALKOXY; R4 IS HYDROGEN OR LOWER ALKYL; R5 IS HYDROGEN, ALKYL, ETHYL CYCLOALKYL, LOWER ALKENYL, HALOGENATED LOWER ALKYL, CYCLOALKYL HAVING 3 TO 6 CARBON ATOMS, INCLUSIVE, PINOYL 2,4-DICHLOROPHENOXYMETHYLENE, BENZYL, PHENYL, OR SUBSTITUTED-PHENYL IN WHICH THE SUBSTITUENTS ARE HALOGEN, NITRO, LOWER ALKYL, LOWER ALKOXY OR TRIHALOMETHYL; Z IS HALOGEN, LOWER ALKYL, NITRO, AMINO OR TRIFLUOROMETHYL, AND M IS AN INTEGER HAVING A VALUE FROM 0 TO 4, INCLUSIVE, PROVIDED THAT WHEN R1, R2, R3 AND R4 ARE EACH HYDROGEN, X AND Y ARE EACH OXYGEN AND M IS O, THEN R5 IS OTHER THAN METHYL OR ETHYL. THE COMPOUNDS ARE USEFUL AS HERBICIDES AND THEY EXHIBIT BOTH PRE-EMERGENCE AND POST-EMERGENCE ACTIVITY. REPRESENTATIVE COMPOUNDS ARE: 1-(3&#39;&#39;-ISOBUTYRAMIDOPHENYL)-3-METHYL UREA, 1-CYCLOHEXYL-3-(3&#39;&#39;-PROPIONAMIDOPHENYL)UREA, 1-BUTYL-3-(3&#39;&#39;-PROPIONAMIDOPHENYL)UREA, 1-BUTYL-3-(3&#39;&#39;-ISOBUTYRAMIDOPHENYL)UREA, 1-(3&#39;&#39;-NITROPHENYL)-3-(3&#39;&#39;-ISOBUTYRAMIDOPHENYL)UREA, 1-N,N-DIMETHYL-3-(PIVALAMIDOPHENYL)UREA, 1-(3&#39;&#39;-PROPIONAMIDOPHENYL)-3-N-BUTYL THIOUREA, AND 1-(3&#39;&#39;-PESTAFLUOROPROPIONAMIDO PHENYL)3,3-DIMETHYL UREA.

United States Patent Int. Cl. C07c 119/20 US. Cl. 260-453 R 6 ClaimsABSTRACT OF THE DISCLOSURE Meta-anilide urea compositions have theformula:

x R, NR N in which X and Y are, independently, oxygen and sulfur; R ishydrogen or lower alkyl; R and R are, independently, hydrogen, alkyl,lower alkoxy, haloalkyl, lower alkenyl, cycloalkyl having from 3 to 6carbon atoms, inclusive, carbalkoxyalkyl, furfuryl, naphthyl, phenyl orsubstituted-phenyl, inclusive, in which the substituents are halogen,nitro, or lower alkoxy; R, is hydrogen or lower alkyl; R is hydrogen,alkyl, ethyl cycloalkyl, lower alkenyl, halogenated lower alkyl,cycloalky having 3 to 6 carbon atoms, inclusive, pinonoyl2,4-dichlorophenoxymethylene, benzyl, phenyl, or substituted-phenyl inwhich the substituents are halogen, nitro, lower alkyl, lower alkoxy ortrihalomethyl; Z is halogen, lower alkyl, nitro, amino ortrifluoromethyl, and m is an integer having a value from 0 to 4,inclusive, provided that when R R R and R are each hydrogen, X and Y areeach oxygen and m is 0, then R is other than methyl or ethyl. Thecompounds are useful as herbicides and they exhibit both pre-emergenceand post-emergence activity. Representative compounds are:

1-(3-isobutyramidophenyl)-3-methyl urea,1-cyclohexyl-3-(3'-propionamidophenyl)urea,1-butyl-3-(3-propionamidophenyl)urea,1-butyl-3-(3'-isobutyramidophenyl)urea,1-(3'-nitrophenyl)-3-(3-isobutyramidophenyl)urea,1-N,N-dimethyl-3-(pivalamidophenyl)urea,1-(3'-propionamidophenyl)-3-n-butyl thiourea, and1-(3'-pestafluoropropi0namido phenyl)3,3-dimethyl urea.

This is a division of application Ser. No. 23,021, filed Mar. 26, 1970,now US. Pat. 3,642,891, which is a continuation-in-part of copendingapplication Ser. No. 746,- 007, filed July 19, 1968, now abandoned,which in turn is a continuation-in-part application of Ser. No. 662,573,filed Aug. 23, 1967, now abandoned.

This invention relates to certain novel meta-anilide ureas which areuseful as herbicides. More specifically, this invention relates tocertain substituted organo-anilide ureas and to the preparation andutility of the compounds as herbicides.

"ice

The compounds of the present invention correspond to the formula:

in which X and Y are independently selected from the group consisting ofoxygen andsulfur, R is hydrogen or lower alkyl, R and R areindependently selected from the group consisting ,of hydrogen, alkyl,lower alkoxy, haloalkyl, lower alkenyl, cycloalkyl having from 3 to 6carbon atoms, inclusive, carbalkoxalkyl, furfuryl, naphthyl, phenyl,substituted-phenyl in which said substituents are selected from thegroup consisting of halogen, nitro, and lower alkoxy; R is hydrogen orlower alkyl; R is selected from the group hydrogen, alkyl,ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, cycloalkylhaving from 3 to 6 carbon atoms, inclusive, pinonoyl, 2,4-dichlorophenoxymethylene, benzyl, phenyl, substitutedphenyl in whichsaid substituents are selected from the group consisting of halogen,nitro, lower alkyl, lower alkoxy and trihalomethyl; and Z is selectedfrom the group consisting of halogen, lower alkyl, nitro, amino andtrifluormethyl, and m is an integer having a value from 0 to 4,inclusive, preferably 0 to 2, inclusive, provided that when R R R and Rare each hydrogen, X and Y are both oxygen and m is 0, then R is otherthan methyl or ethyl.

As employed in this specification, the terms lower alkyl and loweralkoxy preferably include those members of the group containing from 1to 6 carbon atoms, inclusive, in either a straight chain or a branchedchain configuration. Similarly, the term alkyl preferably includes thosemembers of the group containing 1 to 10 carbon atoms, inclusive. Theterm lower alkenyl preferably includes those members of the groupcontaining at least one olefinic bond and containing from 2 to 4 carbonatoms, inclusive. The term carbalkoxyalkyl preferably includes thosemembers of the group containing from 3 to 6 carbon atoms, inclusive. Theterm halogen, as employed herein and in the terms haloalkyl, halogen,halogenated, trihalomethyl, preferably includes fluorine, chlorine andbromine.

The compounds of the present invention are prepared by several methods.Two such methods applicable in preparing the compounds is thecondensation between the appropriate meta-amino substituted anilide witheither an isocyanate or carbamoyl chloride and also the condensation ofthe appropriate meta-amino urea and either an acyl halide or acidanhydride. These methods will be further exemplified below. Similarly,an isothiocyanate is employed to prepare the thiourea derivatives. Whenthe unsubstituted amidophenyl urea is prepared a cyanate salt is reactedwith the appropriate substituted amido aniline. The reactions proceedreadily in the liquid phase. The employment of a solvent is also useful,facilitating processing, as well as agitation of the reactants. Solventssuch as water, benzene, toluene, acetone, tetrahydrofuran, and the like,are employed. A catalyst may be employed to enhance the reactionalthough a catalyst is not required. Catalysts such as e.g. dibutyltindilaurate and anhydrous potassium carbonate and copper powder, areeffective catalysts. The reactions are carried out at temperatures thatpermit operation in the liquid phase. These temperatures are betweenabout room temperature and reflux temperature of the solvent if asolvent is employed. Preferably, the reaction mixture is refluxed at anelevated temperature.

Compounds of the present invention are prepared in accordance with thefollowing illustrative examples.

EXAMPLE 1 Preparation of 1-(3-isobutyramidophenyl)- B-methyl ureaMeta-amino isobutyranilide, 12.5 g. (0.07 mole) is dissolved in 100 ml.of acetone containing a few drops of dibutyltin dilaurate. Methylisocyanate, 4.4 g. (0.077 mole), is added to the mixture. The mixture isrefluxed for two hours. On cooling, the crystalline product is filteredE and dried. There is obtained 8.2 g. (50 percent of theory) of thetitle compound, M.P. 168-171 C.

EXAMPLE 2 Preparation of 1-(3-pivalamidophenyl)-3,3- dimethyl ureaEXAMPLE 3 Preparation of l-(3'-propionamidophenyl)-3- n-butyl thioureaMeta-propionamidonaniline, 8.2 g. (9.05 mole) is dissolved in 50 ml. ofacetone. To this solution is added 5.8 g. of n-butylisothiocyanate. Theresulting mixture is refluxed for two hours. After cooling, it is pouredon to crushed ice and washed with water. After filtering,

the product is dried in vacuum. There is obtained 13.8 g. (98.5 percentof theory) of the title compound, M.P. 136138 C.

EXAMPLE 4 Preparation of 3'-propionamidopheny1 ureaMeta-propionamidoaniline, 8.2 g. (9.05 mole) is dissolved in 100 ml. ofdilute hydrochloric acid solution. Potassium cyanate, 4.1 g. isdissolved in 20 ml. of water and this is added to the above acidsoluiton. The result ing mixture is maintained at 30-40" C. for threehours. After cooling, the crystals are filtered and washed with water.They are dried further in vacuum. There is obtained 8.9 g. (86 percentof theory) of the title compound, M. P. l88-190 C.

EXAMPLE 5 Preparation of 1-(3'-butyramidophenyl)-3-methyl ureaN-Meta-aminophenyl-N'-methyl urea, 11.5 g. (0.07 mole) is suspended in100 ml. of ether and 11.1 g. of nbutyric anhydride containing 5 drops ofconcentrated sulfuric acid is added dropwise. The mixture is heated atreflux for 1 hour. The mixture is cooled and the product filtered off.The product is washed successively with dilute (5%) sodium hydroxide,dilute (5%) HCl, and water and then dried. There is. obtained 11.2 g.(68 percent of theory) of the title compound, M.P. 158- 159 C.

EXAMPLE 6 Preparation of 1-(3'-cyclohexanecarboxamidophenyl)- 3-methylurea N-Meta-aminophenyl-N-methyl urea 11.5 g. (0.07 mole) dissolved inacetone containing 7.7 g. (0.076 mole) of triethylamine and 11.3 g. ofcyclohexane carbonyl chloride is added dropwise with stirring. Theproduct precipitates from the acetone and is filtered off, washed withwater and then dried. There is obtained 16.0 g. (83 percent of theory)of the title compound, M.P. l-193 C.

The following is a table of the compounds which are prepared accordingto the aforementioned procedures. Compound numbers have been assigned tothem and are used for identification throughout the balance of thespecification.

TABLE I x /R NR1H N\ l zm I:

NR4 C-R I Compound number 1 1 Ra Z C oooooooooooooooooooooooooooo 4oooooooooooooooooooooooooooo mmmmmmmmmmmmmmmmmmmmmmmmmmmm wmmmmmmmooommmmmmmmmmmmmmmmom w Footnotes at end of table.

TABLE ICont1nued Compound number R: R3 R4 R5 Z M.P C

29 H 3-NOz-pheny1 H 1-CaH1- 201-203 O H CH H 12-011 164-166 0 H 1-0311 Ht-CiFh 179-181 O H H t-CA'FH 218-221 O CH; t-CA'Fl'n 181-186 S H CQHa-136-168 S H 02115.- 189-190 0 H CHzC(0151:)-.- 181-183 0 H CHzC (CH1);174-177 0 CH3 C Ch 169-173 0 CH3 CFz- 178-184 0 CH n-CgH'I- 133-136 0CH; CH2O-2,4-di Cl-phenyl 146. 418 O C(CHa): 56-61 0 C (CHOL 7L =1.5158O C (CHa)x- D O C(CHa) O C (CHsh. 0 CH3). O CH(CH3)C:H1 O CH(CH3) CaHv-O CH(CH:) C;H7 O CH(CH3) CzH1- O CH(CHa) C 111- 0 CH(CH3)CzH1 0 CH(CH: C111- :)2 1 C(CHahCflED" :)2 :H1-

ooooooooooooooooooooooooooooooooooooooooooooooooooooooooowooooooooooo'ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooeoooo 1'4mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmu:mmmmmmmmmmmmgmmmmmmmmmmmmmmmmmmummmmmmmmmmmmmmmmmmmmmmmmmFootnote at end of table.

mmmmmmmmmmmmmmmmmmmmmammmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmommmmmgmmmmmmmmmmmmgmmmmmmmmmmg CH(CH )C:H5 6-01 179-198 i-GQFII 6-C1126-128 09H 200.5-2045 C(CH3)2C;H1 66-70 CH2CH2C(CH3): CH2CH2O(CH:):ll-CuHy n-CHn n-C 51111. 162-1635 CHzCH(CHa)z 14-21455 CHzCHzCEKCHa);166-167 5 CH=C 160-165 CH=C(OHa)z. nD =L5453 Cyc1opropy1 197-201Cyclohexyl 190-193 CHzO-2,4-diCl-pheny1. 226-231 C(CHahCsH-l 142-147CH2C(CH:): 166-169 H 106-112 CT-h 138-141 n-C3H 139-142 CH=C(CH3)2 68-73CHzCEKCHa); 113-116 CH2C(C1 T=1 73-78 00 113-115 nn lmelting point, C.

C(CH3)C1H1 1.5648 00H: 1.5425 CF: 207-211 CH2CH=CH2-.-. 174-181C(CH3)2CH2C1- 68-72 CH2CH(CH:4)2.. 167-1685 CH(CzH )2 133.5-137 5CHgCl-ilrcyclopent l 197-200 C CHMOHwHm CH(CH3)CH: 9 OfizCHz-cyclohexyl189-191 CHzCH(CHz) CHzCKJHs): 71-75 Pinony 164-167 C(CH:4)3-

zFs. C1115 116-121 G- 21192 CH2CH(CHa)CzH5 139-142 C011 -138 2F5-.177-180 CO1: C(h 195-196 CB1(CHa)2 121 C(CHQzOHzCl 131-136CH2CH(CH3)C2H5- 138-140 CHC(CH3)zOzHa 163-166 CH(C2H5) 162-164CH7CH(CH3)CH:C(CH3)3 132-135 C012 -159 CH2CH(CH3)C2H5 136-138CHzC(CH3)2C2H5 137-140 CH(C2H5)C4HQ-- -162 CH(C2H5)C4H0 -167 CC12CF=151-154 CClzCF1 105-110 C2Fs 194-196 2-OH3-pheny1 159-160 TABLEIIContinued Pre-emergence Post-emergence Compound number:

TABLE IIContinued l 2l=85100% control of all seven plant species testedpreemergence; 18=85100% control of all six plant species testedpostemergence.

HERBICIDAL SCREENING TESTS As previously mentioned, the novel compoundsherein described are phytotoxic compounds which are useful and valuablein controlling various plant species. Compounds of this invention aretested as herbicides in the following manner.

Pre-emergence herbicide test.O-n the day preceding treatment, seeds ofseven different weed species are planted in individual rows using onespecies per row across the width of the Hat. The seeds used are hairycrabgrass (Digitaria sanguinalis (L.) Sc0p.), yellow foxtail (Setariaglauca (L.) Beauv.), watergrass (Eichinachloa crusgalli (L.) Beauv.),California red oat (Avena sativa (L.)), redroot pigweed (Amaranthu'sretroflexus (L), Indian mustard (Brassica juncea (L.) Coss.) and curlydock (Rumex crispus (L). Ample seeds are planted to give about 20 to 50seedlings per row, after emergence, depending on the size of the plants.The flats are watered after planting. The spraying solution is preparedby dissolving 50 mg. of the test compound in 3 ml. of a solvent, such asacetone, containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate).The following day each flat is sprayed at the rate of 20 pounds of thecandidate compound per gallons of solution per acre. An atomizer is usedto spray the solution on soil surface. The flats are placed in agreenhouse at 80 F. and watered regularly. Two weeks later, the degreeof weed control is determined by comparing the amount of germination andgrowth of each weed in the treated flats with weeds in several untreatedcontrol flats. The rating system is as follows:

=no significant injury (0-15 percent control) +=slight injury (2535percent control) ++=moderate injury (55-65 percent control) =severeinjury or death (-100 percent control) An activity index is used torepresent the total activity on all seven weed species. It is the sum ofthe number of plus marks, so that an activity index of 21 representscomplete control of all seven weeds. The results of this test arereported in Table II.

Post-emergence herbicide test.Seeds of five weed species including hairycrabgrass, watergrass, wild oats, Indian mustard, and curly dock and onecrop pinto beans (Phaseolus vulgaris), are planted in flats as describedabove for pre-emergence screening. The flats are placed in thegreenhouse at 72-85 'F. and watered daily with a sprinkler. About 10 to14 days after planting when the primary leaves of the bean plant arealmost fully expanded and the first trifoliate leaves are just startingto form, the plants are sprayed. The spray is prepared by weighing out50 mg. of the test compound, dissolving it in 5 ml. of acetonecontaining 1 percent Tween 20' (polyoXy-ethylene sorbitan monolaurate)and then adding ml. of water. The solution is sprayed on the foliageusing an atomizer. The spray concentration is 0.5% and the rate would beapproximately 20 lb./acre if all of the spray were retained on the plantand the soil, but some spray is lost so it is estimated that theapplication rate is approximately 12.5 lb./acre.

Beans are used to detect defoliants and plant growth regulators. Thebeans are trimmed to two or three plants per flat by cutting ofl? theexcess Weaker plants several days before treatment. The treated plantsare placed back in the greenhouse and care is taken to avoid sprinklingthe treated foliage with water for three days after treatment. Water isapplied to the soil by means of a slow stream from a watering hosetaking care not to wet the foliage.

Injury levels are made and recorded 14 days after treatment. The ratingsystem is the same as described above for the pre-emergence test where(-1-), and are used for the diiferent levels of injury and control. Theinjury symptoms are also recorded. The maximum activity index forcomplete control of all the species in the post-emergence screening testis 18 which represents the sum of the plus marks obtained with the sixplant species used in the test. The herbicide activlty indices are shownin Table II.

The new compounds of the present invention are used as pre-emergence orpost-emergence herbicides and are applied in a variety of ways atvarious concentrations. In practice, the compounds are formulated withan inert carrier, utilizing methods well-known to those skilled in theart, thereby making them suitable for application as dusts, sprays, ordrenches and the like in the form and manner required. The mixtures canbe dispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil and water, water in oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. The amount applied depends upon the nature of theseeds or plants to be controlled and the rate of application varies fromapproximately 1 to approximately 50 pounds per acre. One particularlyadvantageous way of applying the compound is a narrow band along a rowcrop straddling the row. In practice, the compounds are formulated withan inert carrier utilizing methods well known to those skilled in theart, thereby making them suitable for particular application.

The phytotoxic compositions of this invention are applied to the plantsin the conventional manner. Thus, the solid and liquid composition canbe applied to the plant by the use of, for example, power-dusters, boomand hand sprayers and spraydusters. The compositions can also be appliedfrom airplanes as a dust or a spray because they are effective in verylow dosages. In order to modify or control growth of germinating seedsor emerging seedlings, as a typical example, the dust and liquidcompositions are applied to the soil according to conventional methodsand are preferably distributed in the soil to a depth of at least lz-inch below the soil surface. It is not necessary that the phytotoxiccompositions be admixed with the soil particles and these compositionscan be applied merely by spraying or sprinkling the surface of the soil.The phytotoxic compositions of this invention can also be applied byaddition to irrigation water supplied to the field to be treated. Thismethod of application permits the penetration of the compositions intothe soil as the water is absorbed therein. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example, fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with the abovedescribedcompounds include for example, 2,4-dichlorophenoxyacetic acids,2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acidand the salts, esters and amides thereof; triazine derivatives, such as2,4-bis (3-methoxypropylamino)-6-methylthio-S-triazine;2-chloro-4-ethylamino-G-isopropylamino s-triazine, and 2-ethylamino 4isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as3-(3,4-dichlorophenyl)-1,1-dimethyl urea and3-(p-chlorophenyl)-l,l-dimethyl urea and acetamides such asN,N-diallyl-u-chloroacetamide, N-(a-chloroacetyl)hexamethylene imine,and N,N-diethyl-a-bromacetamide, and the like; benzoic acids such as3-amino-2,5-dichlorobenzoic and; thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S ethyl cyclohexylethyl thiocarbamate, S-ethyl hexahydro-lH-azepine-l-carbothioate and thelike. Fertilizers useful in combination with the active ingredientsinclude for example, ammonium" nitrate, urea and superphosphates. Otheruseful additaments include materials in which plant organisms take rootand grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constitutingan effective amount in the best mode of administration in the utilitydisclosed is readily determinable by those skilled in the art. Variouschanges and modi- :fications are possible without departing from thespirit and scope of the invention described herein and will be apparentto those skilled in the art to which it pertains. It is accordinglyintended that the present invention shall onl be limited by the scope ofthe claims.

What is claimed is:

1. A compound having the formula in which X and Y are each oxygen, R andR are each hydrogen, R is lower alkoxy containing from 1 to 6 carbonatoms, inclusive, R is alkyl containing 1 to 10 carbon atoms, inclusive,and R is alkyl containing 1 to 10 carbon atoms, inclusive, and m is 0.

2. A compound according to claim 1 in which R is methoxy, R is methyland R is ethyl.

3. A compound according to claim 1 in which R is methoxy, R is methyland R is t-butyl.

4. A compound according to claim 1 in which R is methoxy, R is methyland R is neopentyl.

5. A compound according to claim 1 in which R; is methoxy, R is methyland R is l-methylbutyl.

6. A compound according to claim 1 in which R is methoxy, R is methyland R is 1,1-dimethylbutyl.

References Cited UNITED STATES PATENTS 3,165,549 1/ 1965 Martin et al.71-120 3,184,301 5/1965 Martin et al. 71120 3,205,258 9/1965 Simonian etal 71-120 3,439,018 4/1969 Brookes et al. 71118 3,434,822 3/1969 Wilsonet al 71-120 3,020,142 2/1962 Willard et al. 71118 GLENNON H. HOLLRAH,Primary Examiner US. Cl. X.R.

